EP1558698B1 - Fluorinated surfactants for aqueous acid etch solutions - Google Patents
Fluorinated surfactants for aqueous acid etch solutions Download PDFInfo
- Publication number
- EP1558698B1 EP1558698B1 EP03770349A EP03770349A EP1558698B1 EP 1558698 B1 EP1558698 B1 EP 1558698B1 EP 03770349 A EP03770349 A EP 03770349A EP 03770349 A EP03770349 A EP 03770349A EP 1558698 B1 EP1558698 B1 EP 1558698B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- etch
- etch solution
- solution
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 51
- 239000011260 aqueous acid Substances 0.000 title description 6
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 230000000873 masking effect Effects 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 61
- 229910016855 F9SO2 Inorganic materials 0.000 description 49
- 239000000203 mixture Substances 0.000 description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 37
- 239000007787 solid Substances 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 27
- 229910052710 silicon Inorganic materials 0.000 description 27
- 239000010703 silicon Substances 0.000 description 27
- -1 fluoride compound Chemical class 0.000 description 25
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- 229910021641 deionized water Inorganic materials 0.000 description 20
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 20
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- 239000002904 solvent Substances 0.000 description 11
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- 238000004140 cleaning Methods 0.000 description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 9
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
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- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
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- 239000000463 material Substances 0.000 description 7
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- 235000012431 wafers Nutrition 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
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- 238000004821 distillation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- FUVKFLJWBHVMHX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FUVKFLJWBHVMHX-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 102100021669 Stromal cell-derived factor 1 Human genes 0.000 description 4
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- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
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- 125000005842 heteroatom Chemical group 0.000 description 3
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- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 2
- CCCYGFBNAZKKTO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n-propylbutane-1-sulfonamide Chemical compound CCCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCCYGFBNAZKKTO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
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- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- PSBKYMODPYHLAW-UHFFFAOYSA-N octan-4-amine Chemical compound CCCCC(N)CCC PSBKYMODPYHLAW-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical class F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
Definitions
- the present invention is directed to certain fluorinated surfactants, and use thereof in aqueous acid etch solutions.
- the etch solutions are used with a wide variety of substrates, for example, in the etching of silicon oxide-containing substrates.
- microelectronic devices such as integrated circuits, flat panel displays and microelectromechanical systems
- new business and consumer electronic equipment such as personal computers, cellular phones, electronic calendars, personal digital assistants, and medical electronics.
- Such devices have also become an integral part of more established consumer products such as televisions, stereo components and automobiles.
- These devices in turn contain one or more very high quality semiconductor chips containing many layers of circuit patterns.
- processing steps are required to convert a bare silicon wafer surface to a semiconductor chip of sufficient complexity and quality to be used, for example, in high performance logic devices found in personal computers.
- the most common processing steps of semiconductor chip manufacture are wafer-cleaning steps, accounting for over 10% of the total processing steps.
- These cleaning steps are normally one of two types: oxidative and etch (or both).
- oxidative cleaning steps oxidative compositions are used to oxidize the silicon or polysilicon surface, typically by contacting the wafer with aqueous peroxide or ozone solution.
- etching compositions are used to remove native and deposited silicon oxide films and organic contaminants from the silicon or polysilicon surface before gate oxidation or epitaxial deposition, typically by contacting the wafer with aqueous acid. See, for example, L.A. Zazzera and J.F. Moulder, J. Electrochem. Soc., 136, No. 2, 484 (1989 ). The ultimate performance of the resulting semiconductor chip will depend greatly on how well each cleaning step has been conducted.
- Microelectromechanical systems are small mechanical devices that can be made using traditional integrated circuit manufacturing techniques. Typical devices include motors, gears, accelerometers, pressure sensors, actuators, mirrors, biochips, micropumps and valves, flow sensors and implantable medical devices and systems.
- the manufacture of MEMS may result in a chip, or die, which contains the moving pieces of the device made from silicon or polycrystalline silicon (polysilicon) encased in silicon oxide.
- the die can also contain the circuitry necessary to run the device.
- release-etch One of the final steps in the manufacture of silicon-based MEMS is commonly referred to as “release-etch” and consists of an aqueous etch utilizing hydrofluoric acid (HF) to remove the silicon oxide to free, or “release”, the silicon or polysilicon pieces and allow them to move.
- HF hydrofluoric acid
- the composition of choice has been dilute aqueous hydrofluoric acid (HF) and, to a lesser extent, hydrochloric acid (HCl).
- HF hydrofluoric acid
- HCl hydrochloric acid
- semiconductor fabricators employ an "HF-last" etch cleaning process consisting of an etching step using dilute aqueous HF to etch oxides.
- aqueous hydrogen fluoride or a mixture with an onium fluoride complex may be used as an etchant.
- the onium fluoride present serves to adjust the etching rate and stabilize the solution to variation in HF concentration.
- buffered oxide etch solutions, or BOEs have a high surface tension and, as a result, may not adequately wet a substrate or penetrate microscopic surface features.
- the present invention provides an aqueous etch solution comprising an acid; and a surfactant of the formula: R f -Q-R 1 -SO 3 - M + (I) wherein R f is a C 1 to C 12 perfluoroalkyl group, R' is -C n H 2n (CHOH) o C m H 2m -, wherein n and m are independently 1 to 6, and o is 0 or 1, and wherein R' optionally contains a catenary oxygen or nitrogen atom; M + is a cation; and Q is -O-, or -SO 2 NR 2 -, wherein R 2 is H, an alkyl, aryl, hydroxyalkyl, aminoalkyl or sulfonatoalkyl.
- the solution may further comprise an onium fluoride compound, such as ammonium fluoride, and may further comprise a second fluorinated surfactant, such as perfluoroalkylsulfonamid
- the fluorinated surfactant is sufficiently stable in the aqueous acid etch solution, and advantageously reduces the surface tension thereof so that nanoscale features may be effectively provided to a silicon substrate, such as an integrated circuit and is soluble in the aqueous acid solution.
- the solution of the instant invention provides one or more of the following advantages; the solution has the same etch rate as conventional etch solutions, possesses low surface tension resulting in low contact angles between the solution and substrate. In addition it is non-foaming, low in particulates that may contaminate a substrate and leaves low or no surface residues on rinse. It also offers improved stability of performance when filtered or after extended storage and affords excellent substrate surface smoothness.
- the etch solution of the present invention is particularly suitable for the etching of oxidized silicon substrates, where the acid is hydrofluoric acid (HF) and/or an onium fluoride complex thereof.
- the acid is hydrofluoric acid (HF) and/or an onium fluoride complex thereof.
- Other substrates, including metals and oxides may also be etched and cleaned by appropriate selection of acid or mixtures of acids.
- this invention relates to an etch solution useful in semiconductor and integrated circuit manufacture, the composition comprising a fluorinated surfactant, hydrogen fluoride and/or onium complex thereof.
- the present invention provides an aqueous etch solution useful for etching, and removal of residues, that contains a relatively low concentration of surfactant, but effectively wets the substrate and has an efficient rate of etching.
- Substrates useful in the present invention include silicon, germanium, GaAs, InP and other III-V and II-VI compound semiconductors. It will be understood, due to the large number of processing steps involved in integrated circuit manufacture, that the substrate may include layers of silicon, polysilicon, metals and oxides thereof, resists, masks and dielectrics.
- the present invention is also particularly useful in the etch and release of silicon-based microelectromechanical (MEMS) devices. The etch cleaning and drying of MEMS has similar issues to those for semiconductor chip manufacture.
- MEMS microelectromechanical
- this invention relates to an etch process for substrates by contacting a substrate with a homogeneous etch solution comprising the fluorinated surfactant and acid for a time sufficient to achieve a predetermined degree of etching.
- this invention relates to a etch process for substrates by contacting an oxidized silicon substrate with a homogeneous etch solution comprising the fluorinated surfactant, HF and/or onium fluoride complex for a time sufficient to achieve a predetermined degree of etching.
- the present invention provides an etch solution with low surface tension that easily penetrates the intricate microstructures and wets the surfaces on silicon substrates.
- the etch process may further comprise the step of rinsing the etch solution from the surface of the etched substrate, and the step of drying the substrate.
- the present invention provides a buffered oxide etch solution (BOE, also known as buffered hydrogen fluoride or BHF) comprising an aqueous solution of the above-described fluorinated surfactant, hydrogen fluoride and ammonium fluoride.
- BOE buffered oxide etch solution
- Such solutions are particularly useful in etching of oxidized silicon due to the high SiO 2 /Si etch selectivity.
- alkyl refers to straight or branched, cyclic or acyclic hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, sec-pentyl, and the like.
- Alkyl groups include, for example, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or preferably 1 to 6 carbon atoms.
- aryl refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl.
- perfluoroalkyl refers to a fully fluorinated monovalent straight or branched, cyclic or acyclic, saturated hydrocarbon radical such as, for example, CF 3 -, CF 3 CF 2 -, CF 3 CF 2 CF 2 -, (CF 3 ) 2 CFCF 2 CF(CF 3 )CF 2 -, CF 3 CF(CF 2 CF 3 )CF 2 CF(CF 3 )CF 2 -, and the like.
- One or more non-adjacent -CF 2 - groups may be substituted with a catenary oxygen or nitrogen atom such as, for example, CF 3 CF 2 OCF(CF 3 )CF 2 -, and the like.
- Perfluoroalkyl groups include, for example, 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms.
- compositions of this invention comprising a fluorinated surfactant, and an acid such as hydrogen fluoride and/or onium fluoride complex, are useful in the various etch operations performed on substrates such as those that may be required for operations in the manufacture of semiconductors.
- substrate will refer to wafers and chips used in semiconductor manufacture, including silicon, germanium, GaAs, InP and other III-V and II-VI compound semiconductors.
- the compositions can effectively convert hydrophilic silicon oxides to soluble or volatile silicon fluorides.
- fluorinated surfactant effectively reduces the surface tension of the aqueous acid, allowing effective wetting of the substrate.
- the etch composition and method of this invention can offer enhanced wetting, which is especially important in small geometry patterns and for features with large aspect ratios, reduced particulate contamination, and reduced surface roughness all leading to improvements in manufacturing efficiency by lowering defects to increase wafer yield, by decreasing cleaning times to increase wafer production or by allowing for longer etch bath life by reducing filtration losses of surfactant.
- the improved performance is due, in part, to the low surface tension of the etch solution due to the fluorinated surfactants used, which contributes to the improved wetting of the surfaces.
- the surface tensions of the etch solutions are generally less than 50 dynes/cm, preferably less than 23 dynes/cm and most preferably between 15 and 20 dynes/cm when measured at 25°C..
- the present invention provides an aqueous etch solution comprising an acid and a surfactant of the formula: R f -Q-R 1 -SO 3 - M + (I) wherein R f is a C 1 to C 12 perfluoroalkyl group, optionally containing catenary oxygen or nitrogen atoms, each R' is independently -C n H 2n (CHOH) o C m H 2m -, wherein n and m are independently 1 to 6, and o is 0 or 1, and wherein R' optionally contains a catenary oxygen or nitrogen atom; M + is a cation; and Q is -O-, or -SO 2 NR 2 -, wherein R 2 is H, an alkyl, aryl, hydroxyalkyl, sulfonatoalkyl or aminoalkyl.
- Q is -SO 2 NR 2 - wherein R 2 is a hydroxyalkyl or aminoalkyl.
- the R f group is a perfluorinated alkyl group having from 1-12 carbon atoms, with 3 to 6 carbon atoms preferred.
- the R f perfluorinated alkyl groups may be unbranched, branched, or acyclic, cyclic and preferably are unbranched.
- Catenary heteroatoms such as divalent oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain, (i.e. replace one or more non-adjacent -CF 2 - groups).
- R f is or contains a cyclic structure, such structure preferably has 5 or 6 ring members, 1 or 2 of which can be catenary heteroatoms.
- the alkylene radical R f is also free of ethylenic or other carbon-carbon unsaturation: e . g ., it is a saturated aliphatic, cycloaliphatic or heterocyclic monovalent group.
- the R 2 group of -SO 2 NR 2 - may be an H, an alkyl, hydroxyalkyl, aminoalkyl, or a sulfonatoalkyl group of the formula -R 1 -SO 3 - M + .
- R 2 may be an alkyl group of the formula -C p H 2p+1 , a hydroxyalkyl group of the formula -C p H 2p -OH, or an aminoalkyl group of the formula -C p H 2p -NR 3 R 4 , a sulfonatoalkyl group of the formula -C p H 2p -SO 3 - , where p is an integer of 1 to 12, preferably 1 to 6, and R 3 and R 4 are independently H or alkyl groups of 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.
- the R 2 group may also comprise an aryl group having from 5 to 12 ring atoms, for example phenyl or naphthyl rings.
- aryl groups such as alkyl substituted aryl groups of the formula C p H 2p+1 -(Aryl)- are also contemplated, as are arylalkylene groups of the formula -C p H 2p -(Aryl).
- the invention therefore provides etch solutions comprising fluorinated surfactants of the formula: wherein R f , R' and M + are as previously defined, p is 1 to 6, Ar is an aryl group, and Z is H, -OH, -SO 3 - , an aryl group (Ar), or -NR 3 R 4 , where R 3 and R 4 are independently H or alkyl groups of one to six carbon atoms.
- fluorinated surfactants contain perfluorooctyl moieties, such as the perfluorooctanesulfonate anion (PFOS). It has been reported that certain perfluorooctyl-containing compounds may tend to bio-accumulate in living organisms; this tendency has been cited as a potential concern regarding some fluorochemical compounds. For example, see U.S. Patent No. 5,688,884 (Baker et al. ). As a result, there is a desire for fluorine-containing surfactants which are effective in providing desired performance, and which eliminate more effectively from the body (including the tendency of the composition and its degradation products).
- PFOS perfluorooctanesulfonate anion
- compositions of the present invention comprising a perfluorobutyl moiety, such as CF 3 CF 2 CF 2 CF 2 -, are expected to eliminate from the body more effectively than perfluorohexyl- and much more effectively than perfluorooctyl-.
- preferred embodiments of the R f group in Formula I include perfluoroalkyl groups, C m F 2m+1 - containing a total of 3 to 6 carbon atoms.
- the indicated alkylene group may further contain a catenary (i.e. in chain) oxygen or nitrogen group whereby a -CH 2 - group is replaced by -O- or - NR 5 -, wherein R 5 is an H-, or a C 1 to C 6 alkyl group.
- the catenary nitrogen group may be a quaternary amine group of the formula --N(R 5 ) 2 + -- , where each R 5 group is independently an alkyl group of 1 to 6 carbons.
- catenary amine groups may include, for example -NH-, -N(CH 3 )-, -N(C 3 H 6 )-, -N(CH 3 ) 2 + -, -N(CH 3 )(C 4 H 9 ) + - and the like.
- the catenary amine group may comprise an in-chain secondary, tertiary or quaternary nitrogen atom. It is preferred that such catenary atoms are not alpha to a -(CHOH)- group, if present and are not alpha to a heteroatom, such as is found in the Q group and -SO 3 - group of Formula I.
- M + represent an inorganic or organic cation.
- Suitable inorganic cations include metal cations, including transition metal cations, alkali- and alkaline earth metal cations and ammonium cations such as NH4 + .
- Suitable organic cations include onium cations such as ammonium, including primary, secondary, tertiary and quaternary ammonium cations, as well as sulfonium, and phosphonium cations.
- ammonium cations especially NH 4 + and quaternary ammonium cations are preferred.
- materials of the invention are prepared by first generating an anion from the appropriate fluorochemical moiety in a polar solvent.
- the anion is typically generated in-situ by reaction of the appropriate fluorochemical moiety with either a strong base, or a fluoride ion.
- a fluoroalkoxide anion of the formula R f -O - is generated by treating the corresponding acid fluoride (R f -CO-F) with fluoride ion.
- a sulfonamide salt may be generated by reacting a compound of the formula R f -SO 2 NR 2 H with strong base to form a nitrogen-centered anion of the formula R f -SO 2 N - R 2 .
- These anions may be further reacted with an electrophile containing either a sulfonate group, or containing a nascent sulfonate group (i.e. a sultone) resulting in compositions of the invention. Further details regarding the preparation of compounds of Formula I may be made with reference to the examples.
- the HF may be aqueous HF per se (i.e. diluted 49% HF), or may be used in the form of an onium fluoride complex.
- onium poly(hydrogen fluorides) have the general formula BH + (HF) x F - where B is an electron-pair donor base and x is an integer generally from 1 to 10, and include oxonium-, ammonium-, pyridinium-, and phosphonium- poly(hydrogen fluorides).
- Such onium complexes are less volatile, less corrosive, and are normally liquids at room temperatures. Many such onium complexes are stable liquids that resist the loss of HF even during distillation.
- the HF useful in compositions and processes of this invention is preferably substantially free of other contaminants such as metals, particulates and non-volatile residues in order to effectively etch the silicon surface at the maximum rate during the manufacturing process and not leave residues.
- the etch solution may be prepared by combining, in any order, the acid (the aqueous hydrogen fluoride and/or the onium fluoride complex in the case of silicon substrates) and the fluorinated surfactant.
- the concentration of hydrogen fluoride may vary widely, i.e. from 0.1 to 49 wt.%, depending on the substrate and the etch rate desired. Generally, the concentration of HF is form about 0.1 to 10 wt.%. If an onium fluoride complex, such as ammonium fluoride, is substituted for all or part of the HF, the amount of the onium fluoride may be determined by the HF acid equivalent.
- the etch solution may further comprise an organic solvent.
- an organic solvent may improve the performance, particularly the post-filtration performance, of the etch solution by improving the solubility of the fluorinated surfactant in the aqueous HF solution. It is believed that organic solvents may advantageously lower the critical micelle concentration of the surfactant.
- Useful organic solvents may include polar solvents such as ethers, such as diethyl ether or tetrahydrofuran, polyethers such as glymes, alcohols, esters, dimethylformamide, acetonitrile, acetone, dimethylsulfoxide and carbonates. Solvent selection may be made by reference to Shah, et al., Semiconductor International, October 1988 .
- the etch solution may further comprise a second surfactant, in addition to the surfactant of Formula I.
- second surfactants include both fluorinated and non-fluorinated surfactants such as are known in the etching art. Reference may be made to Kikuyama et al., IEEE Transactions on Semiconductor Manufacturing, Vol. 3, 1990, pp 99-108 .
- the second surfactant may comprise 0 to 80 weight % of the total surfactant; the total amount of first and second surfactants comprising 10 to 1000 parts per million.
- a particularly useful class of second surfactants is perfluoroalkylsulfonamido salts, including those of the formula: R f -SO 2 N - -R 6 M + (II) wherein R f is a C 1 to C 12 perfluoroalkyl group as previously described for the surfactants of Formula I, R 6 is H, an alkyl group, an aryl group, a hydroxyalkyl group or an aminoalkyl group each having one to six carbon atoms, or an aryl group having 6 to 12 ring atoms, and M + is a cation.
- R 6 is H or a hydroxyalkyl group, and preferably M + represents an ammonium cation, including NH 4 + , and primary, secondary, tertiary and quaternary ammonium cations.
- Etch solutions containing mixtures of the fluorinated surfactant of Formula I and perfluoroalkylsulfonamido salts have been found to provide lower surface tension solutions than can be achieved using either surfactant alone.
- Fluorochemical sulfonamides corresponding to Formula II may be prepared as described in U.S. 4,370,254 (Mitschke et al. )
- the invention provides a process for etching a substrate by contacting the substrate with the etch solution of the invention for a time and at a temperature sufficient to effect the desired degree of etching.
- the substrate is an oxidized silicon substrate and the etch solution is a buffered oxide etch solution as described herein. Normally an oxidized silicon substrate is etched at 15 to 40°C.
- the etch process may further comprise the step of rinsing the etch solution from the etched substrate.
- the solution may be rinsed with water, and preferably deionized water.
- the etch solution is slowly replaced with deionized water in a gradient etch process.
- the etch process may further including a drying step whereby the rinse solution is removed from the surface of the etched substrate such as by the application or heat, forced air, immersion in a solvent bath, such as an alcohol bath, or immersion is the heated vapors of a solvent such as an alcohol.
- a drying step whereby the rinse solution is removed from the surface of the etched substrate such as by the application or heat, forced air, immersion in a solvent bath, such as an alcohol bath, or immersion is the heated vapors of a solvent such as an alcohol.
- buffered oxide etch solutions may comprise 0.1 to 10 weight % HF and 20 to 40 weight % of ammonium fluoride. Such solutions will generally have pH values of from 2 to 7.5.
- the surfactant is used in amounts sufficient to reduce the surface tension of the solution to the desired degree.
- the surfactant is generally used in amounts sufficient to reduce the surface tension of the resulting solution to 50 dynes/cm or less, preferably 23 dynes/cm or less.
- the solution comprises 10 to 1000 parts per million of surfactant, and is preferably 100 to 500 parts per million. Below 10 parts per million the solution may not exhibit the desirable reduced surface tension and large contact angle on silicon substrate. Above 1000 parts per million, there is little improvement in the properties of the solution or the performance in etching.
- the buffered oxide etch solution comprising an aqueous solution of fluorinated surfactant, hydrogen fluoride and onium fluoride, preferably ammonium fluoride, may be used to etch the surface of a silicon wafer.
- the solution may be used to etch a SiO 2 surface having a resist mask.
- Conventional buffered oxide etch solutions often failed to wet, and subsequently etch, fine features of such devices leading to defects.
- BOE etchants are used in standard oxide etch processes in the IC and MEMS manufacture. While the isotropic etching behavior of BOE can limit its utility, the high selectivity for etching of silicon oxide (SiO 2 ) over silicon (Si) is a tremendous advantage over dry etching processes, such as reactive ion etch (RIE). Conventional BOE solutions fail to fully flow into the small contact holes and some of the oxide remains, thereby creating defects.
- RIE reactive ion etch
- substrates may also be etched by appropriate selection of the acid or acid mixture.
- Gold, indium, molybdenum, platinum and nichrome substrates may be etched with a mixture of hydrochloric and nitric acids.
- Aluminum substrates may be etched with a mixture of phosphoric and nitric acids, and may optionally include acetic acid as a buffer.
- Silicon substrates may be etched with a mixture of hydrofluoric, nitric and acetic acids. In general, the fluorinated surfactant is used in amounts described for the buffered oxide etch previously described.
- a SIRTL etch solution may be prepared using a mixture of chromium trioxide and hydrofluoric acid to determine defects in single crystal silicon.
- C 4 F 9 SO 2 NH(CH 2 ) 3 N(CH 3 ) 2 can be prepared essentially according to US Pat. No. 5,085,786 (Alm et al. ) replacing C 6 F 13 SO 2 F with C 4 F 9 SO 2 F.
- C 4 F 9 SO 2 NH(C 2 H 5 ) can be prepared essentially according to WO 01/30873 A1 , Example 1A, replacing NH 2 CH 3 with an equimolar amount of NH 2 C 2 H 5 .
- FC-17 can be prepared essentially according to WO 01/30873 A1 Example 1.
- the white solid was isolated by filtration of the MTBE suspension by suction through a sintered glass frit and washing of the precipitate with two 150mL portions of MTBE to remove possible residual soluble starting materials.
- the solid was dried partially by suction and then further dried in a vacuum oven at 50-60°C, 10 -2 torr for about one hour.
- a white crystalline solid was obtained (13.75 g; 66% yield).
- the 1 H NMR spectrum recorded at 200 MHz in d 6 -acetone was consistent with the structure of C 4 F 9 SO 2 N(C 2 H 5 )C 3 H 6 SO 3 Li.
- a 3-necked round bottom flask fitted with a cold finger condenser (-78°C), an overhead stirrer, thermocouple and a plastic tube for gas addition was charged with perfluorobutanesulfonyl fluoride (PBSF; 500.0 g; 1.6 moles; available from 3M Company, St Paul, MN), isopropyl ether (600 mL; available from Sigma-Aldrich) and placed in a bath of room temperature water.
- Ammonia gas (90.0 g; 5.3 mole) was added through the tube over a period of 3 hours at a rate such that dripping off the -78 °C condenser was not observable,.
- the final temperature of the mixture was 13°C.
- the mixture was allowed to stir overnight with warming to room temperature, then the solvent was distilled at atmospheric pressure.
- the temperature setpoint was lowered to 74°C and deionized water added (400 mL) followed by sulfuric acid (100 g conc; 95%) at a rate to maintain the temperature below 85°C.
- the batch was stirred for about 15 minutes then the upper aqueous phase was removed.
- the resulting solids were washed with aqueous sulfuric acid (50.0 g; conc; 95% in 400 mL water), then with deionized water (500 mL).
- C 4 F 9 SO 2 N(C 2 H 4 OH)C 3 H 6 SO 3 Li was prepared essentially according to the procedure described in Preparation 1 with the exception that C 4 F 9 SO 2 NH(C 2 H 5 ) was replaced with C 4 F 9 SO 2 NH(C 2 H 4 OH) (4.2 g; 0.012 moles; as prepared above), and the corresponding amounts of the following were used: LiOH-H 2 O (0.56 g; 0.013 moles), MTBE (50 mL) and 1,3-propanesultone (1.64 g; 0.013 moles). A white crystalline solid was isolated (3.39 g; 58.9% yield).
- C 4 F 9 SO 2 N(C 2 H 4 OH)C 4 H 8 SO 3 Li was prepared essentially according to the procedure described in Preparation 1 with the exception that the corresponding amounts of the following were used: using C 4 F 9 SO 2 NH(C 2 H 4 OH) (4.2 g; 0.012 moles; as prepared above), LiOH H 2 O (0.565 g; 0.013 moles), MTBE(50 mL), and (75mL), and 1,3-propane sultone was replaced with 1,4-butanesultone (1.83 g; 0.013 moles). Additionally, after evaporating most of MTBE by boiling at atmospheric pressure, DME was added and reflux was resumed at 85°C for 1 hour resulting in precipitation of a white solid. The white solid was isolated (1.39 g; 23.5% yield).
- C 4 F 9 SO 2 N(H)C 4 H 8 SO 3 Li was prepared essentially according to the procedure described in Preparation 3 replacing C 4 F 9 SO 2 NH(C 2 H 4 OH) with C 4 F 9 SO 2 NH 2 (15.0 g; 0.05 moles), and the corresponding amounts of the following were used: LiOH-H 2 O (2.32 g; 0.055 moles), MTBE (100 mL), DME (100 mL), and 1,4-butanesultone (7.5g; 0.055 moles). A waxy white solid was isolated (1.57 g; 7% yield).
- FC-7 The procedure described for Preparation of FC-7 was essentially followed, substituting the following amounts of materials: C 4 F 9 SO 2 NH(CH 2 ) 3 N(CH 3 ) 2 (59.5 g; 0.16 moles), CHPS (62.5 g; 0.32 moles), NaOH pellets (13.3 g; 0.34 moles) and deionized water (250 mL), resulting in a solid shown to be the above salt.
- FC-7 The procedure described for Preparation of FC-7 was essentially followed, substituting the following amounts of materials: C 4 F 9 SO 2 NHMe (90.8 g; 0.29 moles), CHPS (62.5 g; 0.32 moles), NaOH pellets (12.5 g; 0.30 moles) and deionized water (100 mL), resulting in a white solid shown to be: C 4 F 9 SO 2 N(Me)CH 2 CH(OH)CH 2 SO 3 Na.
- a one liter flask equipped with an overhead stirrer, thermocouple, reflux condenser and heating mantle was charged with C 4 F 9 SO 2 NHEt (92.0 g; 0.28 moles), NaOH pellets (0.14 g ; 0.35 moles) and deionized water (90 mL) and held at 98°C for 5 hours.
- the batch was cooled to 76°C and CHPS (69.0 g 0.35 moles), and deionized water (20 mL) were added.
- the batch temperature was increased to 100°C and maintained for 18 hours.
- the set point was lowered to 90°C and deionized water (150 mL) was added.
- the batch was allowed to cool with stirring to 40°C. A white solid had formed in the bottom of the flask, and stirring was stopped and the solid was allowed to settle.
- n-perfluorobutyryl fluoride (166.0 g; 0.562 moles; 90% purity), diglyme (150.0 g), Adogen TM 464 (9.0 g), 35g KF (47.0 g; 0.81 moles), and replacing butane sultone with propane sultone (81.0 g; 0.66 moles).
- the batch was allowed to cool with stirring to 40°C, then poured out into a glass pan and dried at 50-60°C overnight.
- the pan contained an off-white solid (133 g) determined to be C 4 F 9 SO 2 N(C 2 H 4 OH)CH 2 CH(OH)CH 2 SO 3 Na. Structure was confirmed using standard lc/ms techniques.
- the surface tension at a 0.2 wt.% in 85% phosphoric acid was 19.4 dynes/cm.
- a premix of each surfactant was made to facilitate the addition of the surfactant to the 500:1 BOE solution.
- Premixes nominally contained 2% surfactant by wt. in water alone, a mixture of isopropanol/deionized water (3:1 by wt.), or a mixture of water, isopropanol /n-butanol / deionized water (5.4:1.7:1 by wt.).
- Table 1 The fluorochemical premix was added to a buffered oxide etch solution (BOE 500:1 Buffered oxide etch solution; available from Ashland Chemical, Dublin, OH) in an amount such that the resulting surfactant concentration was 500 ppm, unless otherwise noted in Table 1.
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US290763 | 2002-11-08 | ||
US10/290,763 US6890452B2 (en) | 2002-11-08 | 2002-11-08 | Fluorinated surfactants for aqueous acid etch solutions |
PCT/US2003/029262 WO2004044092A1 (en) | 2002-11-08 | 2003-09-17 | Fluorinated surfactants for aqueous acid etch solutions |
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EP1558698B1 true EP1558698B1 (en) | 2007-08-08 |
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US (2) | US6890452B2 (ja) |
EP (1) | EP1558698B1 (ja) |
JP (1) | JP4481830B2 (ja) |
KR (1) | KR101003931B1 (ja) |
CN (1) | CN1324111C (ja) |
AT (1) | ATE369409T1 (ja) |
AU (1) | AU2003278831A1 (ja) |
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WO (1) | WO2004044092A1 (ja) |
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US6890452B2 (en) * | 2002-11-08 | 2005-05-10 | 3M Innovative Properties Company | Fluorinated surfactants for aqueous acid etch solutions |
EP1680806A4 (en) * | 2003-10-28 | 2008-07-30 | Sachem Inc | CLEANING SOLUTIONS AND MEDICAMENTS AND METHOD FOR THEIR USE |
TW200533787A (en) * | 2004-02-25 | 2005-10-16 | Mitsubishi Gas Chemical Co | Etching composition for laminated film including reflective electrode and method for forming laminated wiring structure |
US7294610B2 (en) * | 2004-03-03 | 2007-11-13 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
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-
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- 2002-11-08 US US10/290,763 patent/US6890452B2/en not_active Expired - Lifetime
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- 2003-09-17 AT AT03770349T patent/ATE369409T1/de not_active IP Right Cessation
- 2003-09-17 WO PCT/US2003/029262 patent/WO2004044092A1/en active IP Right Grant
- 2003-09-17 KR KR1020057008094A patent/KR101003931B1/ko active IP Right Grant
- 2003-09-17 AU AU2003278831A patent/AU2003278831A1/en not_active Abandoned
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- 2003-09-17 CN CNB038249278A patent/CN1324111C/zh not_active Expired - Fee Related
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DE60315499D1 (de) | 2007-09-20 |
US20040094510A1 (en) | 2004-05-20 |
WO2004044092A1 (en) | 2004-05-27 |
US20050181620A1 (en) | 2005-08-18 |
KR101003931B1 (ko) | 2010-12-30 |
AU2003278831A1 (en) | 2004-06-03 |
JP2006505668A (ja) | 2006-02-16 |
EP1558698A1 (en) | 2005-08-03 |
CN1694940A (zh) | 2005-11-09 |
US6890452B2 (en) | 2005-05-10 |
ATE369409T1 (de) | 2007-08-15 |
CN1324111C (zh) | 2007-07-04 |
US7101492B2 (en) | 2006-09-05 |
JP4481830B2 (ja) | 2010-06-16 |
DE60315499T2 (de) | 2008-04-30 |
KR20050072796A (ko) | 2005-07-12 |
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